JP3237605B2 - Alicyclic (meth) acrylate derivative having 1,2-diol structure and polymer thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel (meth) acrylate derivative and a polymer thereof, and is particularly useful for a resin used for a photoresist material that uses deep ultraviolet light having a wavelength of 220 nm or less as exposure light. It concerns compounds.

[0002]

2. Description of the Related Art In the field of the manufacture of various electronic devices requiring fine processing on the order of half microns as represented by semiconductor devices, there is an increasing demand for higher density and higher integration of devices. Therefore, the demand for photolithography technology for forming fine patterns is becoming more and more severe. In particular, use of photolithography using an ArF excimer laser (193 nm) has recently been considered for the manufacture of a DRAM having an integration degree of 1 Gbit or more that requires a processing technology of 0.18 μm or less [Donald C. et al. Hoffer et al., Journal of Photopolymer Science and Technology (J
ournalofphotopolymer Sci
ence and Technology), 9 volumes (3
No. 387-397 (1996)].

Therefore, development of a resist material corresponding to photolithography using ArF light is desired.
In the development of the resist for ArF exposure, it is necessary to improve the cost performance of the laser because the gas used as the material for laser oscillation has a short life and the laser device itself is expensive. For this reason, there is a high demand for high sensitivity in addition to high resolution corresponding to miniaturization of processing dimensions.

As a method for increasing the sensitivity of a resist, a chemically amplified resist utilizing a photoacid generator as a photosensitive agent is well known. For example, a typical example is disclosed in
No. 27660 describes a resist comprising a combination of triphenylsulfonium hexafluoroarsenate and poly (p-tert-butoxycarbonyloxy-α-methylstyrene). Such chemically amplified resists are now widely used in resists for KrF excimer lasers [for example, Hiroshito,
C. Grant Wilson, American Chemical Society Symposium Series 242, pp. 11-23 (1984)]. A characteristic of the chemically amplified resist is that a proton acid generated by light irradiation from a photoacid generator as a contained component causes an acid-catalyzed reaction with a resist resin or the like by heat treatment after exposure. In this way, the photoreaction efficiency (reaction per photon) is significantly higher than that of a conventional resist having less than 1. At present, most of the developed resists are chemically amplified.

[0005]

However, in the case of lithography using short wavelength light of 220 nm or less typified by ArF excimer laser light, a resist for forming a fine pattern is a new resist which cannot be satisfied with conventional materials. Characteristics such as high transparency to exposure light of 220 nm or less and dry etching resistance are required.

Conventional g-line (438 nm) and i-line (365 nm)
and a resin having an aromatic ring in a structural unit, such as a novolak resin or poly (p-vinylphenol), as a resin component for a photoresist material for a KrF excimer laser (248 nm). , The etching resistance of the resin could be maintained. However, the resin having an aromatic ring has extremely strong light absorption for light having a wavelength of 220 nm or less. for that reason,
Most of the exposure light is absorbed on the resist surface, and the exposure light does not transmit to the substrate, so that a fine resist pattern cannot be formed. For this reason, conventional resins cannot be directly applied to photolithography using short-wavelength light of 220 nm or less. Therefore, a resist material which does not contain an aromatic ring, has etching resistance, and is transparent to a wavelength of 220 nm or less has been desired.

As a polymer compound having transparency to ArF excimer laser light (193 nm) and resistance to dry etching, a copolymer having an adamantyl methacrylate unit as an alicyclic polymer [Takechi et al., Journal of・ Photopolymer Science and Technology (Journal of Photopol)
ymer Science and Technology
gy), 5 (3), pages 439-446 (1992)
Years)] and copolymers having isobornyl methacrylate units [R. D. RD Allen et al., Journal of Photopolymer Science and Technology (Journal of Photopol).
ymer Science and Technology
gy), Volume 8 (No. 4), pp. 623-636 (1995)
Year 9), and Volume 9 (No. 3), pp. 465-474 (19
1996)] has been proposed.

However, the (meth) acrylate derivative having an alicyclic group used in the former resin does not have a polar group (for example, a carboxyl group or a hydroxyl group) having substrate adhesion. Therefore, a homopolymer of a monomer having an alicyclic group has strong hydrophobicity and poor adhesion to a substrate to be processed (for example, a silicon substrate), and it is difficult to form a uniform coating film with good reproducibility. Furthermore, a pattern cannot be formed by exposure because there is no residue in the adamantane-containing residue, isobonyl-containing residue, or menthyl-containing residue unit having dry etching resistance that can exhibit a difference in solubility before and after exposure. Therefore, the former resin can be used as a resist resin component for the first time by forming a copolymer with a comonomer capable of exhibiting a difference in solubility, such as t-butyl methacrylate or tetrahydromethacrylate, or a co-monomer having substrate adhesion such as methacrylic acid. . However, the comonomer content is required to be about 50 mol%, and the dry etching resistance of the comonomer unit is extremely low. Therefore, the dry etching resistance effect of the alicyclic group is significantly reduced, and the practical use as a dry etching resistant resin is poor.

For this reason, a new resist resin material having high light transparency to light of 220 nm or less, high etching resistance, and improved substrate adhesion has been desired.

[0010]

Means for Solving the Problems The inventor of the present invention has made intensive studies to achieve the above object, and has completed the present invention.

That is, the present invention provides a (meth) acrylate derivative represented by the general formula (1) and a polymer obtained by polymerizing the (meth) acrylate derivative represented by the general formula (1), The present invention relates to a polymer obtained by polymerizing the (meth) acrylate derivative represented by 1) and another polymerizable compound.

[0012]

Embedded image (In the above formula, R ¹ is a hydrogen atom or a methyl group;
Is 1, represented by the general formula (2) or (3)
Represents an alicyclic group having a 2-diol structure. )

[0013]

[0014]

Embedded image (In the above formula, R ⁴ represents a hydrogen atom or a methyl group.) A polymer obtained by polymerizing a (meth) acrylate derivative represented by the general formula (1), or a polymer represented by the general formula (1) Specific examples of the polymer obtained by polymerizing the (meth) acrylate derivative and another polymerizable compound include a resin represented by the general formula (5), but are not limited thereto.

[0015]

[0016]

Embedded image (In the above ^{formula, R 1, R 4, R} 9, R 11 are each a hydrogen atom or a methyl group, R ^{1 0} is bridged ring carbon atoms 1 to 13 having a group decomposable by the group decomposable or acid by acid Formula having 1 to 1 carbon atoms having a hydrocarbon group or a carboxyl group
13, a bridged cyclic hydrocarbon group, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. K, m, and n are respectively k + m + n = 1, 0 <k ≦ 1, 0 ≦ m <1, and 0 ≦ n
<An arbitrary number that satisfies 1. The weight average molecular weight of the polymer is 2,000 to 20,000).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ is a hydrogen atom or a methyl group. G is an alicyclic group having a 1,2-diol structure represented by the general formula (2) or the general formula (3).
4-dihydroxytricyclo [5.2.1.0 ^2,6 ] decyl group,
3,4-dihydroxy-dimethyltricyclo [5.2.1.0
^2,6] decyl group, 3,4-dihydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl methyl group, 3,4-dihydroxy-8-methyl-tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10 ] dodecylmethyl group.

[0018]

[Table 1]

In the general formulas (4) and (5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹¹ are a hydrogen atom or a methyl group. R ⁶ and R ¹⁰ are a group capable of decomposing by an acid, a bridged cyclic hydrocarbon group having 7 to 13 carbon atoms having a group decomposed by an acid, or a bridged cyclic hydrocarbon group having 7 to 13 carbon atoms having a carboxyl group. A hydrogen group,
Specific examples of the group decomposed by an acid include a t-butyl group, a tetrahydropyran-2-yl group, a tetrahydrofuran-
2-yl group, 4-methoxytetrahydropyran-4-yl group, 1-ethoxyethyl group, 1-butoxyethyl group,
1-propoxyethyl group, 3-oxocyclohexyl group, 2-methyl-2-adamantyl group, 8-methyl-8
A tricyclo [5.2.1.0 ^2,6 ] decyl group, or 1,2,2
Examples include, but are not limited to, a 7,7-tetramethyl-2-norbornyl group. Specific examples of the bridged cyclic hydrocarbon group having 7 to 13 carbon atoms having a group decomposed by an acid or the bridged cyclic hydrocarbon group having 7 to 13 carbon atoms having a carboxyl group are shown in Table 2. Tricyclo having such a carboxyl group or an ester group [5.2.
1.0 ^2,6 ] decylmethyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, adamantyl group, norbornyl group, methylnorbornyl group, isobornyl group, tetracyclo [4.4.0.1
^2,5 .1 ^7,10 ] dodecyl group, methyltetracyclo [4.4.0.1
^2,5 .1 ^7,10] dodecyl group, and the like, but the invention is not limited to (but R ¹³ in Table 2 is a group decomposable by acid, specific examples, t- Butyl group, tetrahydropyran-2-yl group, tetrahydrofuran-2-
Yl group, 4-methoxytetrahydropyran-4-yl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1
-Propoxyethyl group, 3-oxocyclohexyl group,
2-methyl-2-adamantyl group, 8-methyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl group, or 1,2,7,
Examples include, but are not limited to, 7-tetramethyl-2-norbornyl group. ).

R ⁸ and R ^{12 each} represent a hydrogen atom or a carbon atom
12 hydrocarbon groups, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclohexyl group,
Dimethylcyclohexyl group, tricyclo [5.2.1.0 ^2,6 ]
Decyl group, an adamantyl group, norbornyl group, isobornyl group, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl group, and the like, but is not limited thereto.

In the general formula (4), x, y and z are respectively x + y + z = 1, 0 <x ≦ 1, 0 ≦ y <1, 0
Any number that satisfies ≦ z <1. R ¹ , R ² and R ³ are
This is the same as general formulas (1) and (2).

In the general formula (5), k, m and n are respectively k + m + n = 1, 0 <k ≦ 1, 0 ≦ m <
1, an arbitrary number satisfying 0 ≦ n <1, and R ¹ and R ⁴ are the same as those in the general formulas (1) and (3). The weight average molecular weight of the polymer of the present invention is from 2,000 to 200,000.

[0023]

[Table 2]

[0024]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 3,4-Dihydroxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate

[0026]

Embedded image

In a 500 ml three-necked flask, dicyclopentenyl acrylate (FA-5, manufactured by Hitachi Chemical Co., Ltd.)
11A) 25 g (0.122 mol) are dissolved in 320 ml of dry methylene chloride and cooled with ice. 39.25 g of m-chloroperbenzoic acid was added thereto, and the mixture was stirred for 1 hour under ice-cooling and for 2 hours at room temperature. The precipitated m-chlorobenzoic acid was separated by filtration, and the filtrate was treated with a 10% aqueous sodium bisulfite solution (300%).
and 5% aqueous sodium carbonate solution (200 ml) and saturated saline. After drying the solution over magnesium sulfate,
Methylene chloride was distilled off under reduced pressure to obtain 25 g of 3,4-epoxytricyclodecyl acrylate (yield 9).
3%). Next, 11 g (0.05 mol) of 3,4-epoxytricyclodecyl acrylate is dissolved in 80 ml of tetrahydrofuran and cooled with ice. 40 ml of a 35% aqueous solution of perchloric acid was added dropwise thereto, and the mixture was stirred at room temperature for 2 hours.
200 ml of ether is added to the reaction solution, and the mixture is washed with a 5% aqueous sodium hydrogen carbonate solution until the aqueous layer becomes alkaline. After washing with a saturated saline solution, the organic layer is dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with 100 ml of a mixed solvent of hexane and ethyl acetate (5: 1) to obtain 8 g of the target product, 3,4-dihydroxytricyclodecyl acrylate (viscous liquid, yield). 67
%). ¹ H-NMR (CDCl ₃ ) δ 0.86-2.50
(10H, m), 3.25-3.70 (2H, br),
4.02-4.18 (2H, m), 4.61 (1H,
s), 5.79 (1H, d), 6.08 (1H, d
d), 6.36 (1H, d); IR (KBr) 3400
(ΝOH), 2848, 2940 (νCH), 1712
(ΝC = O), 1614, 1628 (νC = C) cm ⁻¹

Example 2 3,4-Dihydroxytricyclo [5.2.1.0 ^2,6 ] decyl methacrylate

[0029]

Embedded image

As in Example 1, but using dicyclopentenyl methacrylate instead of dicyclopentenyl acrylate (Aldrich Chemical Co., Ind.)
c. Product No. 40967-7) (viscous liquid, total yield 52%). ¹ H-NMR (CDCl ₃ ) δ
0.78-2.54 (10H, m), 1.95 (3H,
s), 3.2-3.75 (2H, br), 4-4.3
(2H, m), 4.62 (1H, s), 5.57 (1
H, s), 6.07 (1H, s); IR (KBr) 34
00 (νOH), 2850, 2940 (νCH), 17
16 (νC = O), 1630 (νC = C) cm ⁻¹

Example 3 3,4-dihydroxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodecylmethyl acrylate

[0032]

Embedded image

10.26 g of lithium aluminum hydride are suspended in 210 ml of dry ether. 8-Carboxymethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene 59g was added dropwise and then stirred for 2 hours at room temperature. Ice water is added to the reaction mixture to decompose unreacted lithium aluminum hydride. Then 400 ml of 10% sulfuric acid are added. After adding 200 ml of ether and separating the aqueous layer, 200 ml of a 3% aqueous sodium carbonate solution,
Wash with saturated saline in order. The organic layer was dried over magnesium sulfate, and distilling off under reduced pressure and ether 8-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-40 g of dodecene were obtained (78% yield). Then 8-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
40 g (0.21 mol) of dodecene, 30.6 g of N, N-dimethylaniline and 50 mg of phenothiazine are dissolved in 120 ml of dry tetrahydrofuran, and cooled with ice. A solution obtained by dissolving 20.93 g of acryloyl chloride in 30 ml of dry tetrahydrofuran is added dropwise thereto. After stirring for 1 hour under ice cooling, the mixture is stirred at room temperature overnight. The precipitated aniline hydrochloride is filtered off, and the filtrate is concentrated under reduced pressure. 200 ml of ether was added to the residue, and the mixture was washed with 300 ml of 0.5N hydrochloric acid, saturated saline, 200 ml of a 3% aqueous sodium hydrogen carbonate solution and saturated saline in this order. The organic layer was dried over magnesium sulfate, and distilling off under reduced pressure and ether, 8-acryloyloxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
35 g of -3-dodecene was obtained (yield 68%). Next, 8-
Acryloyloxymethyl tetracyclo [4.4.0.1 ^{2, 5} .1
30 g (0.123 mol) of ^7,10 ] -3-dodecene are dissolved in 340 ml of dry methylene chloride. There ice cooling m
-39.3 g of chloroperbenzoic acid is added, and the mixture is stirred for 2 hours under ice cooling. The precipitated m-chlorobenzoic acid was separated by filtration, and the filtrate was washed with a 10% aqueous sodium hydrogen sulfite solution (300 ml), a 4% aqueous sodium hydrogen carbonate solution (300 ml) and saturated saline in this order. The organic layer was dried over magnesium sulfate to obtain by distillation under reduced pressure and methylene chloride 3,4-epoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl methyl acrylate 30.2 g ( Yield 94%). Next, 3,4-
Epoxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl methyl acrylate 20g of (0.077 mol) was dissolved in tetrahydrofuran 120 ml, there under ice-cooling 35%
56 ml of perchloric acid aqueous solution is added dropwise.

After stirring at room temperature for 1.5 hours, ether 2
Then, a saturated saline solution and a 5% aqueous hydrogen carbonate solution 30 were added.
It wash | cleans in order of 0 ml and a saturated salt solution. After drying the organic layer over magnesium sulfate, the solvent is distilled off under reduced pressure. The residue hexane / ethyl acetate mixed solvent (5: 1) 3,4-dihydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] of the object by washing with 60 ml × 4 dodecyl methyl acrylate 1
1 g was obtained (viscous liquid, yield 51%). 1H-NMR
(CDCl ₃ ) δ 0.82-2.27 (13H, m);
3.24-3.70 (4H, m), 3.7-4.2 (2
H, m), 5.83 (1H, d), 6.12 (1H, d
d), 6.41 (1H, d); IR (KBr) 3440
(ΝOH), 2856, 2928 (νCH), 1710
(ΝC = O), 1614, 1626 (νC = C) cm ⁻¹

Example 4 3,4-dihydroxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodecylmethyl methacrylate

[0036]

Embedded image

The synthesis was carried out in the same manner as in Example 3 except that methacryloyl chloride was used instead of acryloyl chloride (total yield: 25%). ¹ H-NMR (CDCl ₃ ) δ 0.84-2.
24 (13H, m), 1.95 (3H, s), 3.2-
3.69 (4H, m), 3.68-4.22 (2H,
m), 5.51 (1H, s), 6.05 (1H, s);
IR (KBr) 3442 (νOH), 2858, 292
7 (νCH), 1712 (νC = O), 1628 (νC
= C) cm ^-1

Example 5 3,4-Dihydroxy-8-methyl-tetracyclo [4.
4.0.1 ^2,5 .1 ^7,10 ] dodecylmethyl acrylate

[0039]

Embedded image

[0040] As in Example 3, except 8-carboxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene in place of 8-methyl-8-carboxymethyl tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] -3-dodecene was synthesized using (23% overall yield). 1H-NMR (CDCl ₃ ) δ
0.75-2.3 (15H, m), 3.23-3.68
(4H, m), 3.7-4.2 (2H, m), 5.82
(1H, d), 6.11 (1H, dd), 6.4 (1
H, d); IR (KBr) 3440 (νOH), 285
6, 2928 (νCH), 1712 (νC = O), 16
15,1628 (νC = C) cm ^-1

Example 6 A polymer having the following structure (in the general formula (4), R¹, R^Two,
R^Three, R^FiveIs a hydrogen atom, R ^FiveIs t-butoxycarbonyl
Toracyclo [4.4.0.1^2,5.1^7,10A dodecyl group, x = 0.
65, y = 0.35, z = 0)

[0042]

Embedded image

In a 100 ml eggplant-shaped flask equipped with a reflux tube, 4 g of the vinyl monomer obtained in Example 1 and 3 g of t-butoxycarbonyltetracyclododecyl acrylate were dissolved in 38 ml of dry tetrahydrofuran, and AIB was added thereto.
N189 mg (30 mmol-1) was added, and the mixture was stirred at 60 to 65 ° C under an argon atmosphere. After cooling for 2 hours, the reaction mixture was treated with ligroin / ether (1/1) 40
The mixture is poured into 0 ml, and the deposited precipitate is separated by filtration. Further re-precipitation purification yielded 3.36 g of the desired product (yield 48%). The copolymerization ratio at this time was 65:35 from the integration ratio of 1H-NMR (x = 0.65, y =
0.35). The weight average molecular weight (M
w) is 15700 (in terms of polystyrene) and the degree of dispersion (Mw
/ Mn) was 1.86.

Examples 7 and 8 Polymerization was carried out in the same manner as in Example 6, except that the charge ratio of the monomers was changed. Table 3 below shows the charge ratio of the monomers, the polymerization ratio of the polymer, and the weight average molecular weight.

[0045]

[Table 3] Examples 9 and 10 Polymerization was carried out in the same manner as in Example 6, except that the amount (concentration) of AIBN was changed. Table 4 below shows the copolymerization ratio (x / y) of the polymer,
Shows the weight average molecular weight.

[0046]

[Table 4]Example 11 A polymer having the following structure (in the general formula (4), R¹, R^Two,
R^Three, R^FiveIs a hydrogen atom, R ⁶Is carboxytetracyclo
[4.4.0.1^2,5.1^7,10A dodecyl group, x = 0.65, y =
0.35, z = 0)

[0047]

Embedded image

The synthesis was carried out in the same manner as in Example 6, except that carboxytetracyclododecyl acrylate was used instead of t-butoxycarbonyltetracyclododecyl acrylate. Yield 56%, Mw = 14800, Mw / Mn =
1.89

Example 12 A polymer having the following structure (in the formula (4), R ¹ , R ² ,
R ³ is a hydrogen atom, R ⁵ is a methyl group, R ⁶ is a t-butyl group,
x = 0.65, y = 0.35, z = 0)

[0050]

Embedded image

As in Example 6, except that t-butoxycarbonyltetracyclododecyl acrylate was replaced by t
-Synthesized using butyl methacrylate. Yield 52
%, Mw = 19500, Mw / Mn = 2.02

Example 13 A polymer having the following structure (in the general formula (4), R¹, R^Two,
R^Three, R^FiveIs a hydrogen atom, R ⁶Is t-butoxycarbonylno
Rubornyl group, x = 0.65, y = 0.35, z = 0)

[0053]

Embedded image

[0054] Similarly to Example 6, except t- butoxy instead of carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodecyl group, was synthesized using the t- butoxycarbonyl norbornyl group. Yield 44%, Mw = 17100, Mw / M
n = 1.82

Example 14 A polymer having the following structure (in the general formula (4), R¹, R^Two,
R^Three, R^FiveIs a hydrogen atom, R ⁶Is 3-methyl-3-t-but
Xycarbonyltetracyclo [4.4.0.1^2,5.1^7,10] Dode
A sil group, R⁷Is a methyl group, R⁸Is a hydrogen atom, x = 0.5
5, y = 0.35, z = 0.1)

[0056]

Embedded image

[0057] In 100ml round-bottomed flask with a reflux pipe, and the vinyl monomer 4g obtained in Example 1 t-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl acrylate 3.55 g, methacrylic acid 0.26 g was dissolved in dry tetrahydrofuran (42 ml).
N209mg, 60-65 ° C under argon atmosphere
And stir. After cooling for 2 hours, the reaction mixture was poured into 500 ml of ligroin / ether (1/1), and the deposited precipitate was separated by filtration. Further re-precipitation purification yielded 3.44 g of the desired product (44% yield). Mw = 1380
0, Mw / Mn = 1.94.

Example 15 A polymer having the following structure (in the general formula (5), R ¹ , R ⁴ ,
R ⁹ is a hydrogen atom, R ¹⁰ is t- butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl group, x = 0.6
5, y = 0.35, z = 0)

[0059]

Embedded image

The synthesis was carried out in the same manner as in Example 6, except that the vinyl monomer obtained in Example 3 was used instead of the vinyl monomer obtained in Example 1. Yield 45%, Mw = 14200, M
w / Mn = 1.88

Embodiment 16

Embedded image

In the same manner as in Example 14, except that the vinyl monomer obtained in Example 1 was used instead of the vinyl monomer obtained in Example 1, and tricyclodecyl acrylate (Hitachi Chemical Industry Co., Ltd.) was used instead of methacrylic acid. ) FA-513A)
And synthesized. Yield 52%, Mw = 13500, Mw / M
n = 1.78

(Evaluation of etching resistance of polymer) 2 g of the resin obtained in Example 6 was dissolved in 10 g of ethyl lactate, and then filtered using a 0.2 μm Teflon filter. Next, spin coating is performed on a 3-inch silicon substrate, and 90
Baking was performed on a hot plate at 60 ° C. for 60 seconds to form a thin film having a thickness of 0.7 μm. The obtained film is subjected to DEM451 reactive ion etching (R
IE) The etching rate for CF ₄ gas was measured using an apparatus (etching conditions: Power = 100 W,
Pressure = 5 Pa, gas flow rate = 30 sccm). Table 5 shows the results. Similarly, the etching rate of the resin obtained in Example 16 was measured. As comparative examples, novolak resist (PFI-15A manufactured by Sumitomo Chemical Co., Ltd.), poly (p-vinylphenol) used as a base resin of KrF resist, and a resin having no bridged cyclic hydrocarbon group in its molecular structure. Poly (methyl methacrylate)
The results for the coated films are also shown. The etching rate was standardized for the novolak resist.

[0064]

[Table 5] The above results indicate that the resin used in the present invention has a low etching rate with respect to CF ₄ gas and is excellent in dry etching resistance.

(Evaluation of Transparency of Polymer) 2.5 g of the resin obtained in Example 6 was dissolved in 10 g of ethyl lactate.
Filtration was performed using a 2 μm Teflon filter. Next, spin coating was performed on a 3-inch quartz substrate, and baked on a hot plate at 90 ° C. for 60 seconds to form a thin film having a thickness of 1 μm. The center wavelength of the ArF excimer laser light was 1 for this thin film using an ultraviolet-visible spectrophotometer.
The transmittance at 93.4 nm was measured. Similarly,
The resin obtained in Example 16 was also measured. as a result,
The transmittance of the polymer obtained in Example 6 was 54% / μm, and the transmittance of the polymer of Example 16 was 57% / μm. from this result,
It was confirmed that the polymer of the present invention exhibited transparency usable as a single-layer resist.

(Evaluation of Patterning of Resist Using Polymer) A resist having the following composition was prepared. (A) Polymer (Example 6): 2 g (b) Photoacid generator (triphenylsulfonium triflate (TPS)): 0.02 g (c) Propylene glycol monomethyl ether acetate: 11.5 g

The above mixture was filtered using a 0.2 μm Teflon filter to prepare a resist. The above resist is spin-coated on a 4-inch silicon substrate,
Bake on a hot plate at 20 ° C. for 1 minute to make a film thickness of 0.4
A 5 μm thin film was formed. Then, the formed wafer was allowed to stand still in a contact type exposure experimental machine sufficiently purged with nitrogen.
A mask in which a pattern was drawn with chrome on a quartz plate was brought into close contact with the resist film, and ArF excimer laser light was irradiated through the mask. Immediately thereafter, baked on a hot plate at 95 ° C for 60 seconds, and 2.38% T at a liquid temperature of 23 ° C.
Develop by immersion method in MAH aqueous solution for 60 seconds,
Subsequently, a rinse treatment was performed with pure water for 60 seconds. As a result, only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive pattern was obtained. Similarly, the resist using the polymer obtained in Example 16 was evaluated. Table 6 shows the results of sensitivity and resolution.

[0068]

[Table 6]

From the above results, it was found that the photoresist material using the polymer of the present invention had excellent resolution characteristics. Further, since there was no phenomenon such as pattern peeling, it was confirmed that the substrate had excellent adhesiveness.

[0070]

As is apparent from the above description, the polymer of the present invention is excellent in dry etching resistance and transparency, and the resist material using the polymer of the present invention is excellent in resolution and substrate adhesion. Accordingly, it is possible to form a fine pattern required for manufacturing a semiconductor device.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Etsuo Hasegawa 5-7-1 Shiba, Minato-ku, Tokyo Within NEC Corporation (56) References JP-A-6-116254 (JP, A) JP-A-7 -252324 (JP, A) JP-A-10-330431 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 69/54 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A (meth) acrylate derivative represented by the general formula (1) . Embedded image (In the above formula, R ¹ is a hydrogen atom or a methyl group;
Represents an alicyclic group having a 1,2-diol structure represented by the general formula (3) . ) (In the above formula, R ⁴ represents a hydrogen atom or a methyl group.) Wherein become in claim 1, wherein the (meth) acrylate derivative with each other copolymerization, or by copolymerization of claim 1, wherein the (meth) acrylate derivative and other polymerizable compounds, the weight average molecular weight 2000 A polymer characterized by being 〜200,000. 3. A polymer represented by the general formula (5). Embedded image (In the above formula, R ¹ , R ⁴ , R ⁹ , and R ¹¹ are each a hydrogen atom or a methyl group, and R ¹⁰ is a bridged cyclic group having 7 to 13 carbon atoms having an acid-decomposable group or an acid-decomposable group. C7-C having a hydrocarbon group or a carboxyl group
13, a bridged cyclic hydrocarbon group, R12 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. K, m, and n each represent a ratio of a monomer unit, and k + m + n = 1, 0 <
Any number that satisfies k ≦ 1, 0 ≦ m <1, and 0 ≦ n <1. The weight average molecular weight of the polymer is 2,000 to 2,000.
00).